EP0500721A1 - Poly(ether sulfones) fluorurees - Google Patents

Poly(ether sulfones) fluorurees

Info

Publication number
EP0500721A1
EP0500721A1 EP90917253A EP90917253A EP0500721A1 EP 0500721 A1 EP0500721 A1 EP 0500721A1 EP 90917253 A EP90917253 A EP 90917253A EP 90917253 A EP90917253 A EP 90917253A EP 0500721 A1 EP0500721 A1 EP 0500721A1
Authority
EP
European Patent Office
Prior art keywords
polymer
phenyl
bis
polymers
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90917253A
Other languages
German (de)
English (en)
Inventor
Samuel David Arthur
Andrew Edward Feiring
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0500721A1 publication Critical patent/EP0500721A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones

Definitions

  • the present invention relates to polymers comprising fluorine-containing poly(ether sulfones) and to the aromatic fluorine-containing sulfone monomers used in the preparation of these polymers.
  • Aromatic poly(ether sulfones) are thermally stable, amorphous engineering resins with attractive properties for electronics and other applications. See C. P. Smith, Chemtech, 290-291 (1988). These resins may be prepared by nucleophilic displacement polymerization of bis-phenols with
  • electronegative sulfone group activates the halides to nucleophilic displacement.
  • Other polymers are also prepared by aromatic nucleophilic substitution with activation provided by a ketone function.
  • U.S. Patent 3,941,748 of King issued March 2, 1976 discloses a process for the preparation of an aromatic polymer of recurring units -ArQ- by heating a reaction mixture of an alkali metal fluoride and (a) a halophenol of formula XArQH and/or (b) a mixture of a dihalobenzenoid compound of formula XArX and a dihydric phenol of formula HQArQH in which Ar is a bivalent aromatic residue, Q is an oxygen or sulfur atom, and X is a halogen atom.
  • polyethers by reacting (a) a mixture of a bisphenol and a dihalobenzenoid compound or (b) a halophenol, in which dihalobenzenoid compound or halophenol halogen atoms are activated by ortho or para -SO 2 - or -CO- groups, with an alkali metal carbonate in the presence of an infusible particulate support
  • European Patent Application 243,833 discloses a copolycondensate moulding composition containing polyarylene sulfone and polyarylene ether sulfone units prepared by polycondensation of a bisphenol mixture of bisphenol A; 4,4'-dihydroxydiphenyl sulfone; and other bisphenol and a mixture of
  • Japanese Patent Application J6 2199-622 discloses hydrophilic aromatic sulfone resins
  • hydrophilic compounds having active hydroxy groups to yield ether bonds between the terminal groups of the aromatic polysulfone polymers and the hydrophilic compounds.
  • Japanese Patent Application J5 5165-920 teaches the production of a linear chlorine-containing polyethersulfone polymer by adding an aromatic tri- or tetrahalide of formula (II):
  • X and Y are each H or Cl provided one is Cl, to a mixture of an inert highly polar solvent and a dialkali metal salt of formula (I):
  • Q is a bond, O, S, aliphalic or alicyclic
  • hydrocarbyl and m is 0 or 1.
  • the present invention comprises an aromatic fluorine-containing poly(ether sulfone) polymer having the following repeating unit (I):
  • R f is a straight chain or branched polyfluoro- alkylene of from 1 to about 20 carbon atoms unsubstituted or substituted by one or more ether oxygens;
  • R is an aromatic moiety
  • the present invention further comprises a monomer having the following formula (II):
  • R f is as defined above in formula (I) Detailed Description of the Invention
  • the present invention comprises novel aromatic fluorine-containing sulfone monomers of formula (II):
  • R f is a straight chain or branched polyfluoro- alkylene of from 1 to about 20 carbon atoms; or R f is a straight chain or branched polyfluoroalkylene of from 1 to about 20 carbon atoms substituted by one or more ether oxygens.
  • Such monomers are useful in the synthesis of aromatic fluorine-containing poly(ether sulfone) polymers.
  • the monomers of formula (II) can be prepared by the reaction of sodium p-halobenzenethiolates with ⁇ , ⁇ -diiodoperfluoroalkanes, followed by oxidation of the resulting sulfides to sulfones with chromium trioxide according to the following reaction sequence wherein X is fluorine.
  • the present invention further comprises novel aromatic fluorine-containing poly(ether sulfone) polymers having the following repeating unit (I):
  • Rf is as defined above for formula (II), and R is an aromatic moiety. Examples of R
  • aromatic rings include aromatic rings, fused aromatic rings such as naphthalene, polyphenyls, biphenyls and the like.
  • R may also be
  • G is C(CH 3 ) 2 or C(CF 3 ) 2 .
  • These polymers are prepared by the condensation polymerization of the fluoromonomers of formula (II), or corresponding chloromonomers, with aromatic dihydroxy compounds such as bisphenols, biphenol or hydroquinones according to the following reaction wherein X is fluorine or chlorine:
  • chloromonomer with dihydroxy aromatic compounds may be conducted under a variety of conditions in the presence of a base of sufficient strength to cause substantial ionization of the dihydroxy aromatic compound.
  • Typical bases are the alkali metal
  • Preferred bases are the alkali metal carbonates; the most preferred base is sodium carbonate.
  • the dihydroxy aromatic compound may be converted to its bis-alkali metal salt in a separate step and then reacted with the monomer.
  • the reaction is preferably conducted in a solvent such as a dipolar aprotic organic solvent.
  • a solvent such as a dipolar aprotic organic solvent.
  • Preferred solvents are dimethyl formamide, dimethyl acetamide, diphenyl sulfone and dimethyl sulfoxide, and mixtures of these solvents with each other or other aprotic organic solvents.
  • the most preferred solvent is a mixture of dimethyl acetamide and toluene.
  • the reaction time and temperature may be varied depending on the nature of the base and dihydroxy aromatic compound and the desired polymer molecular weight.
  • high molecular weight polymers from the monomer of formula (II) and dihydroxy aromatic compounds can be achieved in less than about 2 hours at a reaction temperature of about 140°C.
  • a neutralizing agent such as dimethyl sulfate may be added at the end of the reaction time to cap unreacted hydroxy groups.
  • the polymers of this invention are useful for forming molded objects and chemically stable films, such as those used in gas separating membranes and other applications. They typically have a dielectric constant less than 3, a high rate of permeability with high selectivity, as well as excellent
  • Films and membranes made from these polymers are optically clear and colorless.
  • polymerization solvents dimethylacetamide (DMAC) and toluene, used in these examples were distilled under argon at atmospheric pressure, stored under argon until used, and transferred using syringe
  • 1,4-bis(4-fluorophenylthio)perfluorobutane 175 g chromium trioxide and 1.5 L acetic acid was refluxed for 8 hours. An additional 50 g of chromium trioxide were added and reflux was maintained overnight.
  • 1,4-bis(4-fluorophenylthio)perfluorooctane in 100 mL of acetic acid was treated portionwise with 7.0 g chromium trioxide. The solution was refluxed for 3 hours. About 60% of the acetic acid was removed by distillation and the residue was poured into ice water. The aqueous solution was extracted with ether which was washed with water, saturated aqueous Na 2 CO 3 and brine, and evaporated. The residue was dissolved in a boiling mixture of CH 2 Cl 2 and hexane and cooled to 0°C to give 5.9 g (89%) of product, m.p. 109-110°C. 1 H-NMR (CD 2 Cl 2 ) ⁇ 7.4 (m, 4H); 8.1 (m, 4H).
  • a flask equipped for azeotropic distillation and magnetic stirring was dried under nitrogen and charged with 1.7 g powdered potassium carbonate, 1.14 g (0.05 mol) bisphenol-A, 25 mL toluene and 25 mL dimethyl acetamide.
  • the mixture was heated to a pot temperature of 138°C to azeotropically remove water. It was cooled to 75°C and 3.59 g (0.05 mol) of 1,8-bis-(4-fluorophenylsulfonyl)perfluorooctane was added. The resulting mixture was heated to
  • M w 9.8 X 10 5 .
  • Example 6 The procedure of Example 6 on a 0.0027 mol scale was followed. This polymer is insoluble in CH 2 Cl 2 , so it was washed with this solvent and dried, giving 2.17 g (93%) of polymer showing the following properties:
  • Example 6 The procedure of Example 6 was followed on a 0.0029 molar scale giving 1.64 g (85%) of polymer showing the following properties:
  • Example 6 The procedure of Example 6 was followed on a 0.0046 molar scale giving 4.19 g (92%) of polymer showing the following properties:
  • Example 6 The procedure of Example 6 was followed on a 0.0062 molar scale. This polymer is insoluble in
  • fluorinated spacer group lowers the glass transition temperatures of the polymer of Example 6 (123°C) and Example 7 (142°C) as compared to Udel® (195°C).
  • Dielectric properties of the polymer of Example 6 were measured. A film of the polymer was laminated between 1 ounce copper foils at 270°C and 1000 psi, resulting in good adhesion of the film to copper. The laminate was etched on one side to give a serpentine pattern. The dielectric constant and dissipation factor were determined by time domain reflectometry, Measurements were made over the frequency range of 50 MHz to
  • test fixture uses a set of metrology grade, high precision Eisenhart
  • EL 18 manufactured by Cascade Microtech Co. with sexless APC-7 connectors which permit the transition from coaxial to planar geometry while preserving 50 ohm impedance.
  • Electric performance data for the launchers follows: Frequency range - dc to 18 GHz, Insertion Loss -0.10 db max to 10 GHz and 0.25 db max to 18 GHz, VSWR - 1.15:1 max (23 db return loss).
  • the samples for measurement measured 2" x 2" and consisted of a 14 bend serpentine
  • dielectric constant for Udel® is 3.19 (Encyclopedia of Polymer Science and Engineering, 2nd Ed., Mark et al., Eds., Vol. 13, pp. 192-211, Wiley, 1988).
  • Fluorinated poly(ether sulfone) film for gas permeation testing was produced by spreading a chloroform solution (10% w/v) onto a clean glass plate with a doctor knife (15-mil knife clearance). The cast film was allowed to stand covered at room temperature for several hours and was then heated in a vacuum oven (100°C) overnight to remove traces of solvent. The film was stripped from glass by
  • a modified Millipore high pressure filter holder accepting a 47-mm circle of polymer film was used for permeation testing.
  • the filter holder was modified so that the high pressure side could be continuously swept with the feed gas.
  • the film was pressurized with oxygen/nitrogen (21:79 molar volume) at 500 psig and the gas permeation rate was measured by volume displacement at 1 atm of a water droplet in a capillary tube.
  • Permeate gas composition was determined by evacuating the permeate side of the membrane to 5-10 mm Hg with a vacuum pump through a gas chromatograph sample loop (0.10 mL sample volume; Varian 3700 GC with a 6' x 1/8" 60-80 mesh 5A

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Polyethers (AREA)

Abstract

Polymères comprenant des poly(éther sulfones) contenant du fluor et des monomères comprenant des sulfones aromatiques contenant du fluor utilisés dans la préparation de ces polymères.
EP90917253A 1989-11-09 1990-11-09 Poly(ether sulfones) fluorurees Withdrawn EP0500721A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/435,831 US5084548A (en) 1989-11-09 1989-11-09 Fluorinated poly(ether sulfone)
US435831 1989-11-09

Publications (1)

Publication Number Publication Date
EP0500721A1 true EP0500721A1 (fr) 1992-09-02

Family

ID=23730000

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90917253A Withdrawn EP0500721A1 (fr) 1989-11-09 1990-11-09 Poly(ether sulfones) fluorurees

Country Status (4)

Country Link
US (1) US5084548A (fr)
EP (1) EP0500721A1 (fr)
JP (1) JPH05501583A (fr)
WO (1) WO1991007454A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700310A (en) 1995-12-29 1997-12-23 Mg Generon, Inc. Removal of oil from compressed gas with macroporous polymeric adsorbent
US20050130521A1 (en) * 2003-12-10 2005-06-16 Wyner Daniel M. Protective laminates
US20090163692A1 (en) * 2007-12-21 2009-06-25 General Electric Company Aromatic polyethers
CN107074706B (zh) * 2014-10-28 2021-06-29 株式会社Lg化学 用于支化剂的氟系化合物、使用该氟系化合物的聚合物以及使用该聚合物的聚合物电解质膜

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941748A (en) * 1970-08-19 1976-03-02 Imperial Chemical Industries Limited Process for preparing aromatic polymers in presence of alkali metal fluoride
JPS5165920A (ja) * 1974-12-04 1976-06-08 Matsushita Electric Ind Co Ltd Jikihetsudo
US4331798A (en) * 1979-01-18 1982-05-25 Imperial Chemical Industries Limited Production of aromatic polyethers with infusible particulate substance
DE3614753A1 (de) * 1986-04-30 1987-11-05 Basf Ag Hochtemperaturbestaendige copolykondensat-formmassen
JPH02199622A (ja) * 1989-01-27 1990-08-08 Kao Corp 磁気記録媒体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9107454A1 *

Also Published As

Publication number Publication date
JPH05501583A (ja) 1993-03-25
US5084548A (en) 1992-01-28
WO1991007454A1 (fr) 1991-05-30

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